EP1532195B1 - Method of uniformly distributing a substance in a substrate - Google Patents

Method of uniformly distributing a substance in a substrate Download PDF

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Publication number
EP1532195B1
EP1532195B1 EP03765255A EP03765255A EP1532195B1 EP 1532195 B1 EP1532195 B1 EP 1532195B1 EP 03765255 A EP03765255 A EP 03765255A EP 03765255 A EP03765255 A EP 03765255A EP 1532195 B1 EP1532195 B1 EP 1532195B1
Authority
EP
European Patent Office
Prior art keywords
tert
butyl
substance
bis
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP03765255A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1532195A1 (en
Inventor
Matthias Zäh
Alexander Lichtblau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP1532195A1 publication Critical patent/EP1532195A1/en
Application granted granted Critical
Publication of EP1532195B1 publication Critical patent/EP1532195B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the invention relates to a new method for improved distribution of a substance or mixture of substances in a carrier or substrate or in a mixture of different carriers or substrates.
  • the invention likewise relates to the raw, multicomponent compositions, semi-finished products or end articles obtained by this method and also to the micropowders of the substance or mixture of substances that are used in the method.
  • the invention relates in particular to the application of this method to the incorporation of additives into plastics and to the plastics additives micropowders prepared for that purpose.
  • the object of the invention is to achieve a uniform distribution of a relatively small amount of a substance or mixture of substances in a carrier or substrate or in a mixture of different carriers or substrates without complicated engineering steps and to produce homogeneous, multicomponent raw compositions, semi-finished products or end articles by a technically simple and inexpensive method.
  • A a substance or mixture of substances having a particle size ⁇ 50 ⁇ m is applied uniformly to the surface of a carrier or substrate or of a mixture of different carriers or substrates (referred to below as B) having a particle size ⁇ 5 mm and the mixture obtained is subjected to a shape conversion operation with pressure and/or temperature, the viscosity of the mixture during the operation being at least 50 mPas*s.
  • the fine pulverization of the substance A brings it to a size which allows uniform distribution on the surface of the substrate B.
  • the mixture obtained comprising powders having different particle sizes, is converted by pressure and/or temperature into a viscous state (viscosity of at least 50 mPas*s) and is processed to corresponding raw compositions, semi-finished products or end articles.
  • the specific selection of the geometric proportions produces, in comparison with the existing technique, a distribution which is either substantially more homogeneous in its entirety and results in correspondingly positive properties, or leads to the same subsequent properties with less effort.
  • the method of the invention has the effect that substances incorporated as active substances in a substrate develop a better activity as a result of the homogeneous distribution in the substrate, i.e. are effective in smaller amounts than hitherto, and that the effort required to achieve the homogeneous distribution is less than with conventional methods.
  • the present invention comprises the better dispersion of micronized substances into coarsely particulate substrates, while the said technology consists in dispersing ultrafine particles and/or their agglomerates by means of micronized waxes (but with a coarser particle size than the pigments) into coarse substrates.
  • the size ratio of auxiliary to "substrate" is the other way round and in each case three different particle sizes are processed with one another, while in the present invention - except when using mixtures differing in size - only two different particle sizes are combined.
  • the substance A after the shape conversion operation is at least partly to fully dissolved in the substrate B.
  • Substance A can be brought to the desired size range from coarser particles by means of known techniques, by means of energy input.
  • the intention is to take the median value D 50 of the substance A, above and below which half of the larger and smaller particles are situated, respectively, as a measure of the size order, to ⁇ 50 ⁇ m.
  • the median of the particle size, referred to as D 50 represents the figure above and below which 50% of the larger and smaller particles lie.
  • the underlying distribution function is arbitrary (examples and definitions of terms are given in DIN standard 66141) and ought to possess a D 90 , understood as the figure below which 90% of the smaller particles are located, of 100 ⁇ m.
  • This size order of A can also be obtained, however, by construction or by direct preparation or classification of suitable particles.
  • the substance A preferably has a particle size ⁇ 20 ⁇ m, more preferably still a particle size ⁇ 10 ⁇ m.
  • the substance A will generally be present in a size ratio of ⁇ 1:20, preferably of ⁇ 1:50, more preferably of ⁇ 1:100, to the substrate B, the substrate B preferably having a particle size ⁇ 5mm, more preferably ⁇ 2 mm, very preferably ⁇ 1 mm.
  • the application of the substance A to the surface of the substrate B (and its adhesion thereon) is brought about and maintained, depending on material, not only by forces of adhesion but also (in the case of nonconductive substances) by electrostatic charging during the mixing operation.
  • forces of adhesion in the case of nonconductive substances
  • electrostatic charging during the mixing operation.
  • the mixture of A and B is subjected to a shape conversion operation with pressure and/or temperature, leading alternatively to a raw composition, to a semi-finished product or directly to a finished end article.
  • a shape conversion operation with pressure and/or temperature, leading alternatively to a raw composition, to a semi-finished product or directly to a finished end article.
  • any methods of shape conversion which brings the mixture into a viscous state with a viscosity of at least 50 mPas*s, preferably of at least 100 mPas*s, more preferably of at least 200 mPas*s, in particular of at least 500 mPas*s. Mention may be made in this context of extrusion, kneading, sintering, rotational melting, compression moulding, casting, and powder coating.
  • One preferred embodiment of the invention consists in incorporating additives for plastics into the plastics in the form of micropowders.
  • Additives for plastics are normally added as flakes, granules, powders, dispersions or emulsions, but not as micropowders, the preferred use form being selected only from the standpoint of ease of handling, with no difference having been found to date in the activity of the additives.
  • a variety of commercial forms of plastics additives are known: from powder to granules, all forms are represented. For a variety of reasons (occupational hygiene, handling, production processes, mixing with polymer granules, etc.) the trend is increasingly away from powder towards coarser, dust-free commercial forms.
  • Additives however, must be distributed effectively in the plastic and, preferably, dissolved, in order that they can develop their activity uniformly.
  • One preferred subject of the invention is, accordingly, plastics additives and their mixtures in micronized form.
  • micronized form is meant a powder having a particle size ⁇ 50 ⁇ m with a particle size distribution of D 90 ⁇ 100 ⁇ m and D 50 ⁇ 50 ⁇ m, a preferred particle size distribution being between D 90 ⁇ 50 ⁇ m and D 50 ⁇ 20 ⁇ m and, respectively, D 90 ⁇ 30 ⁇ m and D 50 ⁇ 15 ⁇ m.
  • a further subject of the invention is the production of such micronisates by appropriate methods and their use in plastics and rubbers. Preparation takes place by breaking down coarser particles with energy input, such as grinding of a relatively coarse form in mills such as mechanical mills or in an air jet mill (cf. Ullmann's Encyclopedia of Industrial Chemistry; 5th edition, vol. B2: unit operations I; chapter 5: Size Reduction) or by exposure to acoustics or ultrasound or by direct preparation or separation by means of crystallization or by spraying or other known methods or else by constructive methods from smaller particles.
  • the micronisate can also be prepared by separation from a powder mixture (cf. Ullmann's Encyclopedia of Industrial Chemistry; 5th edition, vol. B2: unit operations I; chapter 14 - 23: Solid-Solid Separati on).
  • micropowders of the invention can be incorporated into polymer substrates conventionally; in view of the improved activity, however, other, simplified methods of incorporation are also conceivable.
  • the additives serve to enhance the processing properties of the polymers or else to achieve the desired properties of the end article, as described in the Plastics Additives Handbook from the authors Gumbleter/Müller. Hence deserving of emphasis is the stabilization to light and heat of polyolefins such as polyethylene, polypropylene, etc., but also all other properties described in the abovementioned handbook.
  • One preferred subject of the invention is stabilizers from the class known as HALS. Others are antioxidants, in-process stabilizers, metal deactivators, costabilizers, etc.
  • auxiliaries in the fine powders to allow their industrial preparation, such as grinding assistants or release agents or driers, for example.
  • the two latter auxiliaries are intended to prevent subsequent agglomeration.
  • polymeric materials the following may be mentioned:
  • These polymers may include further additives, such as, for example
  • additives can be added before, together with or after the addition of the micropowders of the invention to the polymers.
  • the addition both of these additives and of the micropowders of the invention can take place in the form of solids, in solution or as a melt, and also in the form of solid or liquid mixtures or masterbatches/concentrates.
  • the micronized product is prepared on the MC 100 mill from Micro-Macinazione S.A.
  • the starting product is supplied to the mill by way of a vibratory chute such that in the end effect the incoming flow of coarse powder corresponds to the outgoing passage of ultrafine powder.
  • the air pressure for operating the mill is set at 7 bar, and then metered addition is commenced.
  • the mill employed possesses a static classifier for separating off the fine fraction, and so further adjustments are not possible. With a throughput of approximately 1 kg per hour the following result was obtained:
  • PP powder 100 parts were mixed with 0.2 phr of Hostavin N 30 powder or with the same amount of micropowder.
  • the powder was kneaded in a laboratory compounder at 200°C and 40 rpm for 10 min.
  • the kneaded powder was then used to produce 100 ⁇ m films on the laboratory press at 190°C, which were illuminated in a Weatherometer (Ci4000).
  • the degradation of the polymer was monitored by means of the increase in the CO number. The longer the time taken to reach a defined CO number, the better the stabilization.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
EP03765255A 2002-07-19 2003-07-17 Method of uniformly distributing a substance in a substrate Revoked EP1532195B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10233078 2002-07-19
DE10233078A DE10233078A1 (de) 2002-07-19 2002-07-19 Verfahren zur gleichmässigen Verteilung einer Substanz in einem Substrat
PCT/IB2003/003446 WO2004009682A1 (en) 2002-07-19 2003-07-17 Method of uniformly distributing a substance in a substrate

Publications (2)

Publication Number Publication Date
EP1532195A1 EP1532195A1 (en) 2005-05-25
EP1532195B1 true EP1532195B1 (en) 2007-11-14

Family

ID=30010267

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03765255A Revoked EP1532195B1 (en) 2002-07-19 2003-07-17 Method of uniformly distributing a substance in a substrate

Country Status (12)

Country Link
US (1) US7671110B2 (ko)
EP (1) EP1532195B1 (ko)
JP (1) JP4615310B2 (ko)
KR (1) KR100965987B1 (ko)
CN (1) CN100384914C (ko)
AT (1) ATE378368T1 (ko)
AU (1) AU2003249465A1 (ko)
DE (2) DE10233078A1 (ko)
ES (1) ES2294325T3 (ko)
HK (1) HK1080878A1 (ko)
TW (1) TWI298077B (ko)
WO (1) WO2004009682A1 (ko)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106117767B (zh) * 2016-06-30 2021-06-15 济南圣泉集团股份有限公司 一种在基材中掺杂石墨烯的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS601229A (ja) * 1983-06-17 1985-01-07 Sumitomo Chem Co Ltd 無機充填剤含有ポリオレフィン材料の製造方法
JPH0196257A (ja) * 1987-10-09 1989-04-14 Masumi Koishi 電気絶縁組成物
AU632686B2 (en) 1990-04-23 1993-01-07 Union Carbide Chemicals & Plastics Technology Corporation Suspensions of polymer additives in functional fluids and thermoplastic resin compositions containing same
DE4301808A1 (de) * 1993-01-23 1994-07-28 Huels Chemische Werke Ag Verfahren zur Einarbeitung von Stabilisatoren in Polykondensate
JP3686101B2 (ja) * 1994-05-17 2005-08-24 出光興産株式会社 絹フィブロイン超微粉末含有熱可塑性樹脂組成物の成形品及び複合成形品
JP4249341B2 (ja) * 1999-07-19 2009-04-02 株式会社プライムポリマー 耐候性に優れたプロピレン系ランダム共重合体組成物及びそれからなるフィルム
AU2002219838A1 (en) 2000-11-14 2002-05-27 Coltec Industrial Products Inc Abrasion-resistant polytetrafluoroethylene tape

Also Published As

Publication number Publication date
TW200413448A (en) 2004-08-01
DE60317517D1 (de) 2007-12-27
US20060110589A1 (en) 2006-05-25
CN1668678A (zh) 2005-09-14
DE10233078A1 (de) 2004-02-05
JP4615310B2 (ja) 2011-01-19
US7671110B2 (en) 2010-03-02
TWI298077B (en) 2008-06-21
DE60317517T2 (de) 2008-10-23
AU2003249465A1 (en) 2004-02-09
JP2005537345A (ja) 2005-12-08
EP1532195A1 (en) 2005-05-25
HK1080878A1 (en) 2006-05-04
ES2294325T3 (es) 2008-04-01
KR20050021531A (ko) 2005-03-07
KR100965987B1 (ko) 2010-06-24
CN100384914C (zh) 2008-04-30
ATE378368T1 (de) 2007-11-15
WO2004009682A1 (en) 2004-01-29

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